JPH0687809A - Production of quaternary ammonium salt - Google Patents

Abstract

PURPOSE:To efficiently obtain a quaternary ammonium salt with high biodegradability, capable of imparting excellent softness and smoothness, by reaction of a specific amidamine with a quaternarizing agent such as an alkyl halide. CONSTITUTION:The quaternary ammonium salt of formula II (e.g. a compound of formula III) can be obtained by reaction of (A) an amidamine of formula I [R<1> and R<2> are each alkyl or hydroxyalkyl; R<3> and R<4> are each (OH- substituted) alkyl or alkenyl] with (B) a quaternarizing agent of formula R<5>X (R<5> is 1-4C alkyl or benzyl; X is halogen, sulfate or 1-4C alkylsulfate) (e.g. methyl chloride, benzyl chloride). The compound of the formula I can be obtained by the following process: a diamine of formula IV is cyanoethylated using acrylonitrile to form an aminonitrile of formula V, which is then hydrogenated using a hydrogenating catalyst to produce a triamine of formula VI, which is then made to react with a fatty acid or its ester of formula R<3>COOR<6> and/or R<4>COOR<6> (R<6> is H or alkyl).

Description

Detailed Description of the Invention

[0001]

FIELD OF THE INVENTION The present invention relates to a method for producing a quaternary ammonium salt. More specifically, the present invention relates to a method for producing a quaternary ammonium salt which can impart excellent flexibility to fibers and flexibility and smoothness to hair and is also excellent in biodegradability.

[0002]

2. Description of the Related Art Most of the products which have hitherto been marketed as a softening agent for fibers or a hair treatment agent are mostly two long-chain alkyls in one molecule as represented by di (hardened tallow alkyl) dimethylammonium chloride. A composition containing a quaternary ammonium salt having a group as an active ingredient. However, such a quaternary ammonium salt having two long-chain alkyl groups in one molecule accumulates with little biodegradation when the residue after treatment is released to the natural world such as rivers. There's a problem. Therefore, various studies have been made, but it cannot be said to be sufficient. The present inventors are known as a cationic activator (see JP-A-53-94688), a general formula (3)

[0003]

[Chemical 3]

(In the formula, R ¹ and R ² are the same or different and are an alkyl group having 1 to 4 carbon atoms or a hydroxyalkyl group,
R ³ and R ⁴ are the same or different and may be substituted by a hydroxyl group, and may be a linear or branched alkyl or alkenyl group having 7 to 35 carbon atoms, R ⁵ is an alkyl group or benzyl group having 1 to 4 carbon atoms, n Represents an integer of 2 to 6, X represents a halogen atom, a sulfate, or an alkyl sulfate having 1 to 4 carbon atoms. It was found that the quaternary ammonium salt represented by the formula (4) is suitable for the above purpose, but its production method has not been established yet.

[0005]

SUMMARY OF THE INVENTION It is an object of the present invention to provide an efficient method for producing a quaternary ammonium salt which can impart excellent flexibility and smoothness and has good biodegradability.

[0006]

Means for Solving the Problems As a result of intensive studies to solve the above problems, the present inventors have found that the quaternary ammonium salt represented by the general formula (3), which exhibits excellent performance, is effective The manufacturing method was found and the present invention was completed. That is, the present invention, the general formula (1)

[0007]

[Chemical 4]

(Wherein R ¹ , R ² , R ³ , R ⁴ and n have the same meanings as described above), the amidoamine represented by the general formula
(2) R ⁵ X (2) (wherein R ⁵ and X have the same meanings as described above), and a quaternizing agent represented by the above formula is reacted.
The present invention provides a method for producing a quaternary ammonium salt represented by (3).

In the above general formulas (1) and (3), R ¹ , R ²
Are the same or different and each represents an alkyl group having 1 to 4 carbon atoms or a hydroxyalkyl group, specifically, methyl,
Examples thereof include groups such as ethyl, propyl, butyl and hydroxyethyl, with a methyl group being preferred. R ³ and R ⁴ are the same or different and have 7 carbon atoms which may be substituted with a hydroxyl group.
~ 35 represents a straight chain or branched alkyl group or alkenyl group, and specific examples include groups such as undecyl, pentadecyl, heptadecyl, nonadecyl, heneicosadecyl, hardened tallow alkyl, hardened palm alkyl, and hydroxyheptadecyl. , And preferably a hardened tallow alkyl group and a hardened palm alkyl group. Fourth represented by general formula (3)
Examples of the quaternary ammonium salt include the following.

[0010]

[Chemical 5]

Examples of the quaternizing agent represented by the general formula (2) used for the quaternization of the amidoamine represented by the general formula (1) include lower alkyl halides such as methyl chloride, benzyl chloride and dimethylsulfate. And di-lower alkyl sulfuric acid.

According to the method of the present invention, the quaternizing agent represented by the general formula (2) is used in an amount of 0.8 to 2.0 times that of the amidoamine represented by the general formula (1) at 0.5 at 70 to 120 ° C. ~ 10 hours,
The reaction is terminated by stirring without solvent or in a solvent such as water, methanol, ethanol or isopropanol. After that, the quaternary ammonium salt represented by the general formula (3) is obtained by post-treatment by a conventional method. Further, if necessary, a quaternary ammonium salt represented by the general formula (3) having a necessary counter ion can be obtained by salt exchange using an ion exchange resin or the like.

The amidoamine represented by the above-mentioned general formula (1), which is a raw material, is produced by the following method shown in, for example, Japanese Patent Application No. 4-240355 related to the application of the present applicant. That is, the general formula (4)

[0014]

[Chemical 6]

Cyanoethylation of the diamine represented by the formula (wherein R ¹ , R ² and n have the same meanings as described above) using acrylonitrile to give a compound of the general formula (5)

[0016]

[Chemical 7]

An aminonitrile represented by the formula (wherein R ¹ , R ² and n have the same meanings as described above) is obtained. continue,
A hydrogenation catalyst is used to carry out the hydrogenation reaction of the aminonitrile represented by the general formula (5), and the general formula (6)

[0018]

[Chemical 8]

A triamine represented by the formula (wherein R ¹ , R ² and n have the same meanings as described above) is obtained. The resulting triamine was added to the general formula (7) and / or (8) R ³ COOR ⁶ (7) R ⁴ COOR ⁶ (8) (wherein R ³ and R ⁴ have the same meanings as described above, R ⁶ Represents H or an alkyl group having 1 to 3 carbon atoms) and performs amidation using a fatty acid or a fatty acid ester to obtain an amidoamine represented by the general formula (1). When R ³ and R ⁴ are different, first, the primary amine moiety of the triamine represented by the general formula (6) is amidated with the fatty acid or fatty acid ester represented by the general formula (7), and then, Formula (8)
A fatty acid or fatty acid ester represented by the general formula (6)
The secondary amine portion of the amine represented by is amidated to obtain the amidoamine represented by the general formula (1).

The structure of the quaternary ammonium salt represented by the general formula (3) can be confirmed by infrared absorption spectrum and nuclear magnetic resonance spectrum.

[0021]

According to the method of the present invention, a quaternary ammonium salt useful as a soft base having excellent flexibility and biodegradability can be easily synthesized.

[0022]

The present invention will be described in more detail with reference to the following examples, but the present invention is not limited thereto.

Reference Example 1 (a) 204 g of N, N-dimethylaminopropylamine was placed in a four-necked flask equipped with a stirrer, a thermometer, and a dropping funnel, and acrylonitrile 106 was added while keeping the liquid temperature at 60 ° C. or lower.
g was added dropwise over 1 hour. After the completion of dropping, aging was carried out for 5 hours at the same temperature. After the aging, the reaction solution was transferred to an autoclave equipped with a stirrer, a thermometer, and a pressure gauge.
Then, Raney Ni30g was added and the hydrogen pressure was 20kg / cm ² · G.
The hydrogenation reaction was carried out for 6 hours while maintaining the above. After completion of the reaction, Raney Ni was filtered and the reaction product was distilled to obtain 180 g of triamine. The boiling point was 86 ° C / 0.2 mmHg. (b) The above triamine (78 g) and octadecanoic acid (285 g) were placed in a four-necked flask equipped with a stirrer, a thermometer, and a dropping funnel, and the temperature was raised to 150 ° C. The amidation reaction was carried out at the same temperature for 12 hours while distilling off the produced water to obtain 350 g of diamidoamine.

Example 1 120 g of the diamidoamine obtained in Reference Example 1 and 12 of methyl chloride were placed in an autoclave equipped with a stirrer, a thermometer, and a pressure gauge.
g and 65 g of isopropanol were added, and the quaternization reaction was carried out at 80 ° C. for 5 hours to distill off the solvent under reduced pressure to obtain 125 g of the desired product. NMR
The following structure was confirmed from the spectrum and IR spectrum.

[0025]

[Chemical 9]

NMR spectrum (CDCl ₃ , internal standard TMS) 2.3 ppm (m, 4H) C H ₂ -CO-NH-, C H ₂ -CO-N, 3.35 ppm (s, 9H)
NC H ₃ ,

[0027]

[Chemical 10]

IR spectrum (KBr tablet) 1645 cm ^-1 , 1550 cm ^-1 Reference Example 2 78 g of triamine obtained in (a) of Reference Example 1 and 170 g of behenic acid were placed in a four-necked flask equipped with a stirrer, a thermometer and a dropping funnel.
Then, the temperature was raised to 150 ° C. 5 hours at the same temperature,
After carrying out an amidation reaction while distilling off the produced water, 100 g of dodecanoic acid was added and the reaction was continued for 10 hours to obtain 310 g of diamidoamine.

Example 2 120 g of diamidoamine obtained in Reference Example 2 and 12 of methyl chloride were placed in an autoclave equipped with a stirrer, a thermometer and a pressure gauge.
g and 65 g of isopropanol were added, and the quaternization reaction was carried out at 80 ° C. for 5 hours to distill off the solvent under reduced pressure to obtain 125 g of the desired product. NMR
The following structure was confirmed from the spectrum and IR spectrum.

[0030]

[Chemical 11]

NMR spectrum (CDCl ₃ , internal standard TMS) 2.25 ppm (m, 4H) C H ₂ -CO-NH-, C H ₂ -CO-N, 3.35 ppm (s, 9
H) NC H ₃ ,

[0032]

[Chemical 12]

IR spectrum (KBr tablet) 1645 cm ^-1 , 1550 cm ^-1

─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. ⁵ Identification code Internal reference number FI Technical display location C07C 235/28 7106-4H 305/06 7419-4H 305/08 7419-4H D06M 13/467

Claims (2)

[Claims] 1. A general formula (1): (In the formula, R ¹ and R ² are the same or different and have 1 to 4 carbon atoms or a hydroxyalkyl group, and R ³ and R ⁴ are the same or different and have 7 to 35 carbon atoms which may be substituted with a hydroxyl group. In a straight chain or branched alkyl group or alkenyl group, n is an integer of 2 to 6), and an amidoamine represented by the general formula (2) R ⁵ X (2) (wherein R ⁵ has 1 carbon atom). ~ 4 alkyl group or benzyl group, X is a halogen atom, sulfate or 1 to 4 carbon atoms
4 shows an alkyl sulphate of 4. ) A quaternary ammonium salt represented by the general formula (3) is characterized by reacting a quaternizing agent represented by the formula (3). [Chemical 2] (In the formula, R ¹ , R ² , R ³ , R ⁴ , R ⁵ , n and X have the same meanings as described above.) 2. The method for producing a quaternary ammonium salt according to claim 1, wherein R ⁵ X is methyl chloride.